Nonlinear absorption and optical limiting of platinum(Ⅱ) terpyridine complexes (<i>Invited</i>)

Wenfang Sun

doi:10.3788/IRLA20201078

Infrared and Laser Engineering, Volume. 49, Issue 12, 20201078(2020)

Nonlinear absorption and optical limiting of platinum(Ⅱ) terpyridine complexes (Invited)

Wenfang Sun

Author Affiliations

Department of Chemistry and Biochemistry, North Dakota State University, Fargo ND 58108-6050, United States

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Figures & Tables(21)

Fig. 1. Representative structures for the most commonly studied square-planar Pt(II) complexes

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Fig. 2. Structures of Pt(Ⅱ) terpyridine acetylide complexes 1-22 with different substituents on the acetylide ligand or on the terpyridine ligand

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Fig. 3. (a) Linear absorption spectra of complexes 1-3 (8.8×10⁻⁵ mol/L) in CH₂Cl₂/CH₃OH (8∶2) in a 2 mm cell, (b) triplet transient difference absorption (TA) spectra of 2 (2.39×10⁻⁵ mol/L) and 3 (2.09×10⁻⁵ mol/L) in a 1-cm cell. The TA spectrum of 1 was similar to that of 2, thus was not shown in Fig.3(b), (c) Z-scan experimental data and fitting curve for 3 in CH₂Cl₂/CH₃OH (8∶2) with a concentration of 3×10⁻⁴ mol/L and a linear transmission of 95% at 532 nm in a 1 mm cell. Figures a and b are modified from Ref. [50] with permission, copyright © American Institute of Physics

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Fig. 4. (a) and (b) Linear absorption spectra of complexes 4-12 (1×10⁻⁵ mol/L) in acetonitrile in a 1 cm cuvette, (c) ns TA spectra of 4, 5, 6 and 10 in acetonitrile in a 1 cm cell (A = 0.4 at 355 nm). See Ref. [51] for the ns TA spectra of 11 and 12 in acetonitrile, (d) time-resolved fs TA spectra of 11 in acetonitrile, (e) optical limiting curves of 4, 5, 10, 11 and 12 in acetonitrile in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 70% in the 2 mm cell. Figures are modified from Refs. [51] and [52] with permission, copyright © Chinese Optical Society and American Chemical Society, respectively

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Fig. 5. (a) Linear absorption spectra of 19-22 (2.0×10⁻⁵ mol/L) in acetonitrile in a 1 cm cuvette, (b) ns TA spectra of 19-22 in acetonitrile in a 1 cm cell (A= 0.4 at 355 nm), (c) optical limiting curves of 19-22 in acetonitrile in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 70% at 532 nm in the 2 mm cell. Figures are modified from Ref. [53] with permission, copyright © American Chemical Society

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Fig. 6. Structures of Pt(N^N^N) complexes 23-32

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Fig. 7. (a) Linear absorption spectra of 23-27 in CH₂Cl₂, (b) ns time-resolved TA spectra of 25 in CH₂Cl₂ in a 1 cm cell (6.2×10⁻⁵ mol/L (A₃₅₅ = 0.888)), (c) ns time-resolved TA spectra of 26 in CH₂Cl₂ in a 1 cm cell (3.9×10⁻⁵ mol/L (A₃₅₅ = 0.564)), (d) optical limiting curves of 25-27 in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 70% at 532 nm in the 2 mm cell. 25 and 26 were dissolved in CH₂Cl₂, and 27 was dissolved in DMF. Figures are modified from Ref. [5] with permission, copyright © American Chemical Society

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Fig. 8. (a) Linear absorption spectra of 28-32 in acetonitrile, (b) ns TA spectra of 28-32 in acetonitrile in a 1 cm cell (λ_ex = 355 nm), (c) optical limiting curves of 28-32 in acetonitrile in a 2 mm cell at 532 nm for 4.1 ns laser pulses. The linear transmission for all solutions was adjusted to 75% at 532 nm in the 2 mm cell. Figures are modified from Ref.[56] with permission, copyright © American Chemical Society

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Fig. 9. Structures of Pt(II) R-fluorenylterpyridine chloride complexes 33-37

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Fig. 10. (a) UV-vis absorption spectra in CH₃CN for 33-35, (b) time-resolved fs transient difference absorption spectra of 33 in CH₃CN, (c) open-aperture Z-scan experimental data and fitting curve for 34 in CH₃CN at 740 nm. The energy used for the experiment was 6.6 μJ, and the beam waist at the focal point was 31 μm. Figures are modified from Ref.[67] with permission, copyright © Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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Fig. 11. (a) UV-vis absorption spectra of 36 and 37 in DMSO, (b) nanosecond TA spectra of 36 and 37 in CH₃CN immediately after laser excitation. λ_ex = 355 nm. A₃₅₅ = 0.4 in a 1 cm cuvette. (c) optical limiting curves of 36 and 37 in DMSO solution for 4.1 ns laser pulses at 532 nm. The linear transmission of the solution was adjusted to 95% in a 2 mm cuvette. The beam waist at the focal plane was 72 μm, (d) wavelength dispersion of the ratios of excited-state absorption cross section to that of the ground-state absorption (σ_ex/σ₀) and TPA cross section (σ₂) for 36 and 37 in DMSO solution. Figures are modified from Ref.[72] with permission, copyright © American Chemical Society

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Fig. 12. Structures of mononuclear or multinuclear alkynylplatinum(Ⅱ) terpyridine complexes 38-44

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Fig. 13. Structures of a trinuclear RuPt₂ and heptanuclear RuPt₆ complexes 45 and 46

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Table 1. Optical limiting parameters at 532 nm for ns laser pulses^a

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Table 1. Optical limiting parameters at 532 nm for ns laser pulses^a

Complexes	F_th/J·cm⁻²	F_throughput/J·cm⁻²	T_lim(at 3.6 J·cm⁻²)
^aModified from Ref. [50] with permission. Copyright © American Institute of Physics
1	0.03	1.07	0.30
2	0.03	1.16	0.32
3	0.02	0.45	0.12

Table 2. Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile^[51,53]

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Table 2. Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile^[51,53]

Complexes	τ_T/ns	σ₀^c/10⁻¹⁹cm²	F_th^d/mJ·cm^-2	T_lim^e	σ_eff/σ₀
^aTriplet excited-state lifetime deduced from the decay of the TA at 700 nm, from Ref.[51]. ^bTriplet excited-state lifetime deduced from the decay of the TA at 680 nm, from Ref.[53]. ^cGround-state absorption cross section at 532 nm, from Refs. [51], [53] or [57].^dRSA threshold when the transmission dropped to 90% of the linear transmission. ^eNonlinear transmittance at high incident fluence. ^fAt incident fluence of 2.5 J/cm². ^gAt incident fluence of 3.0 J/cm². This table is modified from Refs.[51] and [53] with permission. Copyrights © Chinese Optical Society and American Chemical Society, respectively
4	766^a	2.43	48	0.28^f, 0.25^g	>3.57^f, >3.89 ^g
5	659^a	7.18	144	0.34^f	>3.02^f
10	672^a	11.2	1090	0.44^f	>2.30^f
11	62^a	2.50^[57]	62	0.19^f	>4.66^f
12	51^a	2.40	900	0.45^f	>2.24^f
19	255^b	18.1	250	0.27^g	>3.67^g
20	408^b	4.30	370	0.27^g	>3.67^g
21	384^b	17.6	490	0.32^g	>3.19^g
22	2540^b	13.4	52	0.18^g	>4.81^g

Table 3. Photophysical parameters of 28-32 in CH₃CN

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Table 3. Photophysical parameters of 28-32 in CH₃CN

	28	29	30	31	32
^{a 1}MLCT/¹LLCT band maxima. ^bFemtosecond (fs) TA band maxima. ^cSinglet excited-state lifetimes. ^dNanosecond (ns) TA band maxima. ^eTriplet excited-state lifetimes. ^fQuantum yields of the triplet excited-state formation. ^gIntersystem crossing (ISC) time. Data in rows 2 and 5-7 are from Ref. 56; data in rows 3, 4 and 8 are from Ref.[63], copyright © American Chemical Society and Old City Publishing, Inc., respectively
λ_abs/nm^a	463	436	456	463	470
λ_S1-Sn/nm^b	717	685	712	719	766
τ_s/ps^c	37±23	56±17	139±128	42±8	46±16
λ_T1-Tn/nm^d	725	720	755	730	785
τ_T/ns^e	420	660	130	340	130
Φ_T^f	0.65	0.53	0.19	0.64	0.66
τ_isc/ps^g	57	106	732	66	70

Table 4. Ground-state and excited-state absorption cross sections of 28-32 in CH₃CN at 532 nm

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Table 4. Ground-state and excited-state absorption cross sections of 28-32 in CH₃CN at 532 nm

	σ₀^a/10⁻¹⁸ cm²	σ_T^b/10⁻¹⁸ cm²	σ_T/σ₀	σ_TΦ_T/σ₀	σ_s^c/10⁻¹⁸ cm²	σ_s/σ₀	σ_T^d/10⁻¹⁷ cm²	σ_T/σ₀
^aGround-state absorption cross-section. ^bTriplet excited-state absorption cross section deduced from the TA spectrum. ^cSinglet excited-state absorption cross sections obtained from fitting the Z-scan data. ^dTriplet excited-state absorption cross sections obtained from fitting the Z-scan data. Data in columns 2-5 are from Ref.[56]; while data in columns 6-9 are from Ref.[63], copyright © American Chemical Society and Old City Publishing, Inc., respectively
28	1.30	60.1	46.2	30.0	32±2	29.2	12±2	9.2
29	1.07	60.9	56.9	30.2	28±2	26.2	12±1	11.2
30	1.53	160	104.5	19.9	18±1	11.8	14±2	9.2
31	1.69	57.2	33.8	21.6	50±5	29.8	11±1	6.5
32	4.60	45.4	9.9	6.5	30±2	6.5	13±2	2.8

Table 5. Singlet excited-state absorption cross sections of 28 at different wavelengths^a

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Table 5. Singlet excited-state absorption cross sections of 28 at different wavelengths^a

λ/nm	σ₀/10⁻¹⁸ cm²	σ_s/10⁻¹⁸ cm²	σ_s/σ₀
^aObtained from the best-fit of ps Z-scan data, reported in Ref.[63]. Copyright © Old City Publishing, Inc
500	9.18	17.5±0.5	1.9
532	1.30	38±2	29.2
550	0.709	27±1	38.1
570	0.302	15±2	49.7
600	0.096	25±2	260.4

Table 6. Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH₃CN

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Table 6. Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH₃CN

Complex	λ/nm	σ₀ /cm²^a	σ_S /10⁻¹⁸ cm²^b	σ_S/σ₀	σ₂ /GM
^aGround-state absorption cross sections. ^bEffective singlet excited-state absorption cross sections with the assumption of σ_S2 = σ_S. ^cEstimated from the fs TA data at zero time delay. ^dσ_S2 = (12±7)×10⁻¹⁸ cm². This table is modified from Ref.[67] with permission, copyright © Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
33	575	10.1	20±1	2.0
	600	3.83	20±2	5.2
	630	0.956	17±1	18
	670	0.191	25±1	131
	740		24.4^c		850±50
34	550	14.7	38±2	2.6
	575	6.31	24±2	3.8
	600	2.49	24±2	9.6
	630	0.765	26±2	34
	680	0.153	12±1	78
	740		7.7^c		1 200±100
	760		11.1^c		1 000±200
	800		7.7^c		2 000±200
	825		11.6^c		600±100
35	575	25.8	43±5^d	1.7
	600	10.9	36±2	3.3
	630	3.63	20±2	5.5
	670	0.765	16±1	21

Table 7. Photophysical parameters of 36 and 37^a

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Table 7. Photophysical parameters of 36 and 37^a

	λ_abs/nm (ε/L·mol⁻¹·cm⁻¹) ^b	λ_S1-Sn/nm (τ_S/ps) ^b	λ_T1-Tn/nm (ε/L·mol⁻¹·cm⁻¹; τ_T/μs; Φ_T) ^c
^aThis table is modified from Ref.[72] with permission, copyright © American Chemical Society. ^bIn DMSO. ^cIn CH₃CN
36	340 (32550), 378 (20200), 428 (26900)	542 (49.4±18.3)	530 (48560; 3.37; 0.72)
37	345 (39140), 385 (sh. 20140), 433 (27040)	555 (58.7±25.4)	545 (46150; 1.72; 0.58)

Table 8. Absorption cross sections of 36 and 37 at selected wavelengths determined by fitting of Z-scan data

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Table 8. Absorption cross sections of 36 and 37 at selected wavelengths determined by fitting of Z-scan data

λ/nm	σ₀(λ)^a/10⁻¹⁸ cm²		σ_S(λ)/10⁻¹⁸ cm²		σ_T(λ)^c/10⁻¹⁸ cm²		σ_S/σ₀		σ_T/σ₀		σ₂(λ)/GM
λ/nm	36	37	36	37	36	37	36	37	36	37	36	37
^a Deduced from UV-Vis absorption spectrum. ^b Estimated from σ_S(532 nm) and the femtosecond transient difference absorption spectrum at zero time delay. These values are effective cross sections for the singlet excited states because the fs TA includes contributions from both S₁ and S₂ states. ^cσ_T(532 nm) was determined from the combined fitting of nanosecond and picosecond Z-scan data. For other wavelengths, σ_T(λ) was estimated from σ_T(532 nm) and the femtosecond transient difference absorption spectrum at 5.9 ns time delay. ^d Effective TPA cross sections for excited-state-assisted TPA. ^e Effective TPA cross section for the Z-scan of lowest energy (11.5 µJ at 825 nm, 7.9 µJ at 850 nm, 8.3 µJ at 875 nm, and 10.0 µJ at 900 nm). This table is modified from Ref.[72] with permission, copyright © American Chemical Society
480	5.23	−	28	−	28	−	5.35	−	5.35	−	−	−
500	1.41	1.32	22	42	40	14	15.6	31.8	28.4	10.6	−	−
532	0.0955	0.390	42	19	68	21	440	48.7	712	53.8	−	−
550	0.0435	0.187	35	35	66	28	805	187	1517	150	−	−
600	0.0222	0.0726	21^b	40	29	15	946	551	1306	207	50	−
630	0.0076	0.0336	17^b	29^b	23	13	2237	863	3026	387	110	1500
680	~0	0.0153	19b	27^b	23	13	−1765		−	850	160	600
740	~0	0.0084	22^b	28^b	31	15	−3333		−1786		65	550
760	~0	~0	22^b	29^b	36	16	−	−	−	−	90	400
800	~0	~0	22^b	23^b	53	20	−	−	−	−	60	450
825	~0	~0	−	43^b	−	21	−	−	−	−	200^d	500
850	~0	~0	−	−	−	−	−	−	−	−	280^d	3700^e
875	~0	~0	−	−	−	−	−	−	−	−	180^d	3000^e
900	~0	−	−	−	−	−	−	−	−	−	200^d	−
910	~0	~0	−	−	−	−	−	−	−	−	−	1700^e

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Wenfang Sun. Nonlinear absorption and optical limiting of platinum(Ⅱ) terpyridine complexes (Invited)[J]. Infrared and Laser Engineering, 2020, 49(12): 20201078

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Paper Information

Category: 激光与物质相互作用

Received: Sep. 18, 2020

Accepted: --

Published Online: Jan. 14, 2021

The Author Email:

DOI:10.3788/IRLA20201078

Topics

laser devices and laser physics

Lasers and Laser Optics

Laser physics

laser manufacturing

Instrumentation, Measurement and Metrology

Table 1. Optical limiting parameters at 532 nm for ns laser pulsesa

Table 1. Optical limiting parameters at 532 nm for ns laser pulsesa

Table 2. Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile[51,53]

Table 2. Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile[51,53]

Table 3. Photophysical parameters of 28-32 in CH3CN

Table 3. Photophysical parameters of 28-32 in CH3CN

Table 4. Ground-state and excited-state absorption cross sections of 28-32 in CH3CN at 532 nm

Table 4. Ground-state and excited-state absorption cross sections of 28-32 in CH3CN at 532 nm

Table 5. Singlet excited-state absorption cross sections of 28 at different wavelengthsa

Table 5. Singlet excited-state absorption cross sections of 28 at different wavelengthsa

Table 6. Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH3CN

Table 6. Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH3CN

Table 7. Photophysical parameters of 36 and 37a

Table 7. Photophysical parameters of 36 and 37a

Table 8. Absorption cross sections of 36 and 37 at selected wavelengths determined by fitting of Z-scan data

Table 8. Absorption cross sections of 36 and 37 at selected wavelengths determined by fitting of Z-scan data

Table 1. Optical limiting parameters at 532 nm for ns laser pulses^a

Table 1. Optical limiting parameters at 532 nm for ns laser pulses^a

Table 2. Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile^[51,53]

Table 2. Photophysical parameters and optical limiting data for 4, 5, 10, 11, 12, and 19-22 in acetonitrile^[51,53]

Table 3. Photophysical parameters of 28-32 in CH₃CN

Table 3. Photophysical parameters of 28-32 in CH₃CN

Table 4. Ground-state and excited-state absorption cross sections of 28-32 in CH₃CN at 532 nm

Table 4. Ground-state and excited-state absorption cross sections of 28-32 in CH₃CN at 532 nm

Table 5. Singlet excited-state absorption cross sections of 28 at different wavelengths^a

Table 5. Singlet excited-state absorption cross sections of 28 at different wavelengths^a

Table 6. Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH₃CN

Table 6. Excited-state absorption and two-photon absorption cross sections for 33-35 at different wavelengths in CH₃CN

Table 7. Photophysical parameters of 36 and 37^a

Table 7. Photophysical parameters of 36 and 37^a